KR100344327B1 - Multifunctional Fabric Auxiliary Molds and Manufacturing Method Thereof - Google Patents

Abstract

The present invention

10 to 60% by weight of the nonionic surfactant (a) of the general formula (1),

10 to 60% by weight of a reaction product (b) of at least one nonionic surfactant of formula (2) with an ethylenically unsaturated sulfonic acid or carboxylic acid, or anhydrides thereof,

4-20% by weight of hydrotropes (c),

0 to 20% by weight of the nonionic surfactant (d) of the general formula (3),

0-8% by weight of magnesium salt (e) of organic carboxylic acid,

0-30% by weight of a chelating agent or metal ion sequestrant (f),

0-10 wt% of a diol or polyol (g) and

Multifunctional fabric auxiliary formulations comprising 0 to 60% by weight of water (h) but necessarily comprising one of components (e) to (g), methods for their preparation and their use.

In the above formula,

R ₁ to R ₅ , Y ₁ to Y ₄ , “alkylene”, m ₁ , n ₁ , p ₁ and P ₂ are as defined in the specification.

Description

Multifunctional Fabric Auxiliary Formulation and Method for Making the Same

FIELD OF THE INVENTION The present invention relates to aqueous fabric auxiliary formulations of silicone members having low foaming and storage stability, methods for their preparation, and their various uses as stabilizers in wetting agents, detergents, dispersants or peroxide bleach solutions.

The present invention,

10 to 60% by weight of the nonionic surfactant (a) of the general formula (1),

10 to 60% by weight of the reaction product (b) of at least one nonionic surfactant of formula (2) with an ethylenically unsaturated sulfonic acid or carboxylic acid, or anhydrides thereof,

Hydrotropic agent (c) 4 to 20% by weight,

0 to 20% by weight of the nonionic surfactant (d) of the general formula (3),

0-8% by weight of magnesium salt (e) of organic carboxylic acid,

0-30% by weight of chelating agent or metal ion sequestrant (f),

0-10 wt% of a diol or polyol (g) and

A novel textile auxiliary formulation comprising 0 to 60% by weight of water (h), which must include at least one of components (e) to (g).

In the above formula,

R ₁ and R ₂ are each independently C ₈ -C ₂₂ alkyl or C ₈ -C ₂₂ alkenyl,

R ₃ is hydrogen, C ₁ -C ₄ alkyl, a cycloaliphatic radical having 6 or more carbon atoms, or benzyl,

R ₄ is C ₉ -C ₁₄ alkyl,

R ₅ is C ₁ -C ₈ alkyl, alicyclic radical having 5 or more carbon atoms, lower alkylphenyl or styryl,

Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently hydrogen, methyl or edel, provided that one of Y _l , Y ₂ , Y ₃ and Y ₄ must be hydrogen,

"Alkylene" is an alkylene radical of 2 to 4 carbon atoms,

m _l is an integer from 1 to 40,

n ₁ is an integer from 1 to 60,

p _l is an integer from 4 to 10,

p ₂ is an integer of 0 to 8.

Components (a) to (g) may each consist of individual compounds or a plurality of individual compounds.

Since they have a considerably low foaming tendency and good process suppression, the addition of additional antifoams, in particular silicone-containing compounds, to new fabric auxiliary formulations can be ruled out.

Substituents R ₁ and R ₂ in formulas (1) and (2) are each preferably hydrocarbon radicals of saturated or unsaturated aliphatic monoalcohols having 8 to 22 carbon atoms. Hydrocarbon radicals may be straight or branched. Preferably, R ₁ and R ₂ are each an alkyl or alkenyl radical having 9 to 14 carbon atoms.

Aliphatic saturated monoalcohols are suitably not only natural alcohols, including lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, but also 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octane 2-ol, isononyl alcohol, trimethyl hexanol, trimethyl nonyl alcohol, decanol, C ₉ -C _{ll-oxo-alcohol,} tridecyl alcohol, iso-decanol tree or a straight-chain primary alcohols having a carbon number of 8 to 22 (alpol, Synthetic alcohols). Some typical examples of these alpoles are Alpole (8-10), Alpole (9-11), Alpole (10-14), Alpole (12-13) or Alpole (16-18) ("Alpole" is a registered trademark) to be.

Unsaturated aliphatic monoalcohols are typically dodecenyl alcohol, hexadecenyl alcohol or oleyl alcohol.

The alcohol radicals may be present alone or in the form of a mixture of two or more components, typically a mixture of alkyl and / or alkenyl groups derived from soy fatty acids, palm fruit fatty acids or tallow oils.

The (alkylene-0) chain is preferably of the structural formula or Is a divalent radical.

R ₄ is a straight chain hydrocarbon radical of saturated aliphatic monoalcohol having 8 to 14 carbon atoms, typically n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl or n- Tetradecyl.

R ₅ , defined as C ₁ -C ₈ alkyl in formula (3), is methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl or tert-butyl. Preferably R ₅ is n-butyl.

Examples of cycloaliphatic radicals are cycloheptyl, cyclooctyl or preferably cyclohexyl.

Examples of suitable nonionic surfactants as component (a) are 2 to 60 mol, preferably 4 to 10 mol, of alkylene oxides, in particular ethylene oxide (where the ethylene oxide units are each propylene oxide, in particular ethylene oxide (here ethylene oxide) The units may be substituted by substituted epoxides such as propylene oxide and / or 1,2-butylene oxide, respectively) and polyadditions of unsaturated or saturated higher fatty alcohols having 8 to 22 carbon atoms or mixtures of these compounds to be.

Preferred nonionic surfactants of component (a) are at least one compound of the general formula (4).

In the above formula,

R ₆ is C ₈ -C ₁₃ alkyl,

Y ₅ is hydrogen or methyl,

m ₂ is 3 to 15.

Suitable starting monomers for preparing the polymer of component (b) are ethylenically unsaturated monomeric sulfonic acids or carboxylic acids or anhydrides thereof. Monocarboxylic acids and dicarboxylic acids and their anhydrides as well as sulfonic acids may suitably be used, each containing ethylenically unsaturated aliphatic radicals, preferably having up to 7 carbon atoms. Preference is given to monocarboxylic acids having 3 to 5 carbon atoms, for example acrylic acid, methacrylic acid, α -haloacrylic acid, 2-hydroxyethylacrylic acid, α -cyanoacrylic acid, crotonic acid and vinylacetic acid. The ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid and mezaconic acid, citraconic acid, glutaconic acid and methylmalonic acid. Preferred anhydrides of these acids are maleic anhydride.

Suitable monomeric sulfonic acids used in the polymerization reaction are typically vinylsulfonic acid or 2-acrylamido-2-metalpropanesulfonic acid.

The catalyst used in the preparation of component (b) is preferably an initiator which forms free radicals. Examples of suitable initiators for carrying out the radical polymerization reaction are azobis (isobutyronitrile), azobis (2-methylvaleronitrile), 1,1'-azobis (1-cyclohexanitrile) and alkyl 2,2 ' Symmetric aliphatic azo compounds such as azobis (isobutyrate); Symmetric diacyl peroxides such as acetyl peroxide, propionyl peroxide or butyryl peroxide, benzoyl peroxide, bromine-, nitro-, methyl- or methoxy substituted benzoyl peroxide as well as lauryl peroxide; Symmetric peroxydicarbonates such as diethyl, diisopropyl, dicyclohexyl as well as dibenzylperoxydicarbonate; Tert-butyl-N- (phenylperoxy) carbamate or tert-butyl-N- (2, as well as tert-butylperbenzoate, tert-butylperbenzoate or tert-butylphenylperacetate Peroxydicarbamate, such as 3-dichloro- or 4-chlorophenylperoxy) carbamate. Further suitable peroxides are tert-butylhydroperoxide, di-tert-butylperoxide, cumene hydroperoxide, dicumene peroxide and tert-butylperpivalate. Further suitable compounds are potassium persulfate which is preferably used for the preparation of component (b).

The catalyst is usually used in an amount of 0.1 to 10% by weight, preferably 0.5 to 2% by weight, based on the starting materials.

Component (b) is preferably in the form of partially neutralized compounds having a pH of 3 to 6. Polymer preparation typically involves reacting ethylenically unsaturated sulfonic acids or carboxylic acids or their anhydrides in the presence of a mixture of nonionic surfactants or nonionic surfactants of formula (2).

The reaction product is subsequently partially neutralized to pH 3-6, preferably pH 4-5 with inorganic and / or organic bases. Suitable bases are typically from 1 to 8% by weight of inorganic and / or organic bases such as sodium hydroxide, magnesium hydroxide, ethanolamine, triethanolamine, N, N, N, N-detrakis (2-hydroxypropyl) Amylenamine or 1-amino-1-deoxysorbitol or mixtures thereof. Add water to make 100% by weight.

The polymerization reaction is conveniently carried out in an inert atmosphere, for example in the presence of nitrogen.

Component (b) is preferably the reaction product of 45 to 5% by weight of acrylic or methacrylic acid with 5 to 45% by weight of at least one nonionic surfactant of formula (5).

In the above formula,

R ₇ is C ₈ -C ₁₈ alkyl,

Y ₆ is hydrogen, methyl or ethyl,

n ₂ is 1 to 40.

Hydrotropes of component (c) are suitably

General formula [here,

X ₁ is — (CH ₂ ) _1-6 , —CH═CH—CH ₂ — or —O— (CH ₂ ) _2-6 , and R ₈ , R ₉ and R ₁₀ are each independently hydrogen, hydroxy, Halogen or C ₁ -C ₆ alkoxy, examples of the compounds of formula (6) are benzyl alcohol, 2,4-dichlorobenzyl alcohol, phenylethanol, phenoxyethanol, 1-phenoxy-2-propanol (phenoxy -Isopropanol) and cinnamil alcohol;

Sulfonates of terpenoids or mononuclear or dinuclear aromatic compounds (eg sulfonates of camphor, toluene, xylene, cumene and naphthol);

Aliphatic saturated and unsaturated C _{1 -11} -monocarboxylic acids (for example acetic acid, propionic acid, hexanoic acid or undecylenic acid) or

Saturated or unsaturated C ₃ -C ₁₂ dicarboxylic acids or C ₃ -C _l2 polycarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid and sebacic acid, undecano Acid and dodecanedicarboxylic acid, fumaric acid, maleic acid, tartaric acid and malic acid, as well as citric acid and aconitic acid).

All the aforementioned organic acids may be present in the form of their water soluble salts, for example alkali metal salts, preferably sodium or potassium salts, or amine salts.

Other hydrotropes useful as component (c) in the practice of the present invention are alkyl sulfates of formula (7).

R ₁₁ O-SO ₃ X ₂ (7)

In the above formula,

R ₁₁ is a saturated branched or straight-chain aliphatic radical having 4 to 24 carbon atoms,

X ₂ is hydrogen, alkali metal or ammonium.

When the alkyl sulphate is in salt form, it is conveniently a sodium, potassium or ammonium salt. Sodium salts are preferred.

Aliphatic saturated radicals R _ll are derived from monoalcohols, suitably natural or synthetic alcohols. Natural alcohols typically include lauryl, myristyl, cetyl, stearyl, arachidyl and behenyl alcohol. Preferred compounds are those in which R ₁₁ has 4 to 12, preferably 4 to 8, branched aliphatic synthetic alcohols such as isobutyl alcohol, secondary-butanol, tert-butanol, isoamyl alcohol, 2-ethylbutanol, 2-methylpentanol, 5-methylheptan-3-ol, 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethyl hexanol, trimethylnonyl alcohol , n-decanol or C ₉ -C ₁₁ oxoalcohols.

Alkyl sulfates may already be in their salt form and may be used alone or together as a technical mixture in the wetting agents of the present invention.

An example of the hydrotrope of general formula (7) is 2-ethylhexyl sulfate.

These alkyl sulfates are prepared by the reaction of suitable alcohols, for example by sulfuric acid, oleum, chlorosulfonic acid or sulfur trioxide, in a known manner.

Further preferred hydrotropes useful in the practice of the present invention are typically sodium lauriniminodipropionate, dihydroxyethyl-resin fatty glycinate, disodium cocoampodiacetate, disodium caprylo ampodiacetate Or preferably an amphoteric surfactant comprising disodium dicarboxyethyl cocopropylenediamine or resin fatty ampopolycarboxy glycinate.

An important nonionic surfactant suitable as optional component (d) is the compound of formula (8).

In the above formula,

R ₁₂ is C ₉ -C ₁₄ alkyl,

R ₁₃ is C ₁ -C ₄ alkyl,

Y ₇ , Y ₈ , Y ₉ and Y ₁₀ are each independently hydrogen, methyl or ethyl, provided that one of Y ₇ , Y ₈ , Y ₉ and Y ₁₀ is necessarily hydrogen,

p ₃ and p ₄ are each independently an integer of 4 to 8.

Examples of end-capped nonionic surfactants of component (d) are C ₁₀ -C _{l 2} fatty alcohols and multiple adducts of ethylene oxide, multiadditions of ethylene oxide and propylene oxide or 1 mol of C ₁₀ fat. A reaction product of an alcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide, these multiadditions may be endblocked with C ₁ -C ₄ alkyl, preferably methyl or butyl, respectively.

The nonionic surfactants of formulas (1) and (2) are in a known manner, typically after reacting a suitable alkylene oxide multiple adduct with thionyl collide, followed by saturation or unsaturated C Prepared by reaction with _8- C ₂₂ monoalcohol.

The terminally blocked nonionic surfactants of formula (3) are inherently known methods, typically reacting a suitable molar ratio of ethylene oxide and / or propylene oxide and / or butylene oxide with 1 mol of alcohol R ₄ -OH. The resulting multiple adducts are then prepared by reacting with alkyl halide R ₅ -Hal, preferably C ₁ -C ₄ alkyl chloride.

Magnesium salts of carboxylic acids with complexing properties useful as component (e) are salts of gluconic acid, citric acid, malic acid, lactic acid, L-glutamic acid and L-aspartic acid.

Preference is given to using magnesium salts of gluconic acid as component (e), most preferably magnesium monogluconate or magnesium digluconate. Magnesium gluconate can be used in itself as a new formulation, preferably as a solid. In a further aspect of the invention, the gluconate may be formed from gluconic acid and magnesium oxide or preferably magnesium hydroxide in the same reaction system. Gluconic acid or its sodium salt can also be used in the form of a mixture with a water soluble magnesium salt. Suitable water soluble magnesium salts here are acetates, most preferably sulfates or heptahydrates thereof, in particular chlorides or hexahydrates thereof. Magnesium salts are commonly used as a solid, in which case solid magnesium chloride hexahydrate is preferred.

Preferred metal ion sequestrants useful as component (f) of the new formulations

A mixture of monomers and oligomers of formulas (9a) and (9b) (f ₁ ),

d-gluconic acid (f ₂ ),

Citric acid (f ₃ ) and

It is a compound selected from aminophosphonic acid (f ₄ ).

In the above formula,

Y ₇ is hydrogen or -COT ₁ ,

R ₁₄ , X ₃ and T ₁ are each independently C ₁ -C ₄ alkyl,

q ₁ is 1-16.

The mixture of monomers and oligomers (f ₁ ) is preferably a mixture of monomers and oligomers of the general formulas (10a) and (10b).

In the above formula,

R ₁₅ is methyl or ethyl,

q ₂ is 1 to 13.

Mixtures of monomers and oligomers of the type indicated above are known per se and are prepared by known methods. Thus, for example, mixtures of formulas (10a) and (10b) are prepared by reacting acetic anhydride, preferably acetic acid, and optionally acetic anhydride, in an aqueous medium. The oligomer component of component (f _l ) is hydrolyzed at least in part to the corresponding monomer in a novel aqueous formulation in the presence of an alkali metal hydroxide. Thus, preferably, one monomer of formula (9a) or (10a) is also suitable as component (f ₁ ) of the novel formulation.

Component (f _l ) is preferably used in the new formulation as an aqueous solution of 35 to 90% by weight, more preferably 40 to 85% by weight and most preferably 40 to 60% by weight.

Examples of component (f ₄ ) include nitrilotrimethylenephosphonic acid, sodium salt of etylenediamine-tetramethylenephosphonic acid, diethylenetriamine-pentamethylenephosphonic acid or sodium salt of N, N-bis (phosphonomethyl) glutamic acid. to be.

Compounds suitable as component (f) act as metal ion sequestrants against alkaline earth metals and heavy metals in aqueous solutions containing per compounds (e.g. hydrogen peroxide) during pretreatment, in particular during cellulosic textile bleaching processes. . In particular, when these components are present, the decomposition of the overcompounds by glass, that is, uncomplexed heavy metal, which may be present in the process water or added alkali of the fiber material is suppressed.

Component (g) may suitably be a dihydric or polyhydric alcohol. Preferred dihydric alcohols are preferably alcohols having 2 to 6 carbon atoms in the alkyl moiety, typically ethylene glycol, 1,2- or 1,3-propanediol, 1,3-, 1,4- or 2, 3-butanediol, 1,5-pentanediol and 1,6-hexanediol or 2-methyl-2,4-pentanediol. Preferably the last mentioned compound is used in a new formulation.

Typical examples of polyhydric alcohols are glycerol, erythritol, pentite (eg arabite, adonite and xylite) as well as hexite (eg D-sorbitol, D-mannitol and dulcitol).

10 to 60% by weight of at least one nonionic surfactant (a) of the general formula (4),

10 to 60% by weight of the reaction product (b) of 5 to 45% by weight of at least one nonionic surfactant of formula (5) with 5 to 45% by weight of acrylic acid,

4-20% by weight of hydrotroping agent (c) selected from sodium cumene-4-sulfonate and dodecyliminodipropionate disodium salt,

0 to 20% by weight of nonionic surfactant (d) of the general formula (8),

0-8% by weight of magnesium monogluconate or magnesium digluconate (e),

0-30% by weight of D-gluconic acid (f), and

Preference is given to using textile auxiliary formulations which comprise 0 to 10% by weight of 2-methyl-2,4-pentanediol (g), but which must comprise at least one of components (e) to (g).

In the above formula,

R ₆ is C ₈ -C ₁₃ alkyl,

R ₇ is C ₈ -C ₁₈ alkyl,

R ₁₂ is C ₉ -C _l4 alkyl,

R ₁₃ is C ₁ -C ₄ alkyl,

Y ₅ is hydrogen or methyl,

Y ₆ is hydrogen, methyl or ethyl,

Y ₇ , Y ₈ , Y ₉ and Y ₁₀ are each independently hydrogen, methyl or ethyl, provided that one of Y ₇ , Y ₈ , Y ₉ and Y ₁₀ is necessarily hydrogen,

m ₂ is 4 to 15,

n ₂ is 1 to 40,

p ₃ and p ₄ are each independently an integer of 4 to 8.

The new textile auxiliary formulations add components (a), (b), (c) and optional components (d), (e), (f) and (g) to water (component (h)) or stir the appropriate components While mixing and adding deionized water until a homogeneous solution is obtained. This process is a pure mechanical process that can be carried out at 30-40 ° C. for elevated temperature and convenience. No chemical reaction occurs.

Another aspect of the present invention for the preparation of novel textile co-formulations is to first prepare monomeric ethylenically unsaturated sulfonic acids or carboxylic acids or anhydrides thereof in one or more nonionic surfactants of general formula (1) and / or general formula (2). And reacting while adjusting the pH to about 4.5 in the presence of a catalyst and then adding the remaining ingredients until a homogeneous solution is obtained to prepare component (b).

Fabric preparation formulations already prepared have a pH of, for example, 2 to 5, preferably 2.5 to 3.5. The pH is always for 1% aqueous solution of the new formulation. Subsequently, the desired pH is adjusted using magnesium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, or triethanolamine, and preferably sodium hydroxide.

The new formulations are single phase silicone-free fabric auxiliary formulations with good chelating properties and metal ion containment properties, antifouling activity and storage stability and low foaming. They are good in emulsifying properties and stable in alkaline liquids. They do not foam in alkaline bleach and do not form deposits. They also have good peroxide stabilizing properties and provide good wetting to the fabric. The formulation can also be readily biodegradable. Because they are in liquid form, they are easy to operate and are particularly suitable for technical surveying devices. These new formulations are suitable for a variety of applications because of their versatility. They can typically be used as wetting agents, textile detergents, dispersants or stabilizers in peroxide bleach solutions. They are also excellently suitable for use as household detergents for all applications.

Accordingly, the present invention also relates to a process for wetting, washing and / or bleaching a fibrous material, including treating the fibrous material in an aqueous medium in the presence of a fabric auxiliary formulation as claimed in claim 1. will be.

The amount of the textile auxiliary formulation of the present invention added to the treatment liquid is 0.1 to 60 g / l, preferably 1 to 20 g / l of the treatment liquid. These liquids may further contain additional components such as desizing agents, dyes, fluorescent brighteners, synthetic resins and alkaline agents such as sodium hydroxide and hydrogen peroxide.

Suitable fiber materials include cellulose, in particular untreated natural cellulose [eg hemp, flax, jute, viscose staples, viscose, acetate rayon, natural cellulose fibers and, preferably, raw cotton, wool, polyamide, polyacrylonitrile or Polyester fibers and knits such as polyacrylonitrile / cotton or polyester / cotton blends.

The fiber material may be present in any of the forms shown. For example, it may be present in the form of coarse stock, yarn, woven fabric or knitted fabric. Thus, the material may typically be in the form of a fabric material made from always a blend of pure cellulosic fabric fibers or cellulosic fabric fibers and synthetic fabric fibers. The fibrous material can be treated in an aqueous liquid either continuously or batchwise.

The aqueous treatment liquid can be applied by impregnating the fibrous material in a known manner for convenience with an absorption of about 70 to 120% by weight on the pad. The pad method is used in particular for pad steam and pad placement processes.

The impregnation process can be carried out at 10 to 60 ° C., preferably at room temperature. After impregnation and expression, the cellulosic material is subjected to any heat treatment process at 80 to 140 ° C. The heat treatment is carried out with steam at 95 to 140 ° C, most preferably 100 to 106 ° C. The heat treatment may take 30 seconds to 60 minutes depending on the heating progress characteristic and the temperature range. In the pad batch process, the impregnated product is dried without drying and packaged in a plastic sheet and stored for 1 to 24 hours at room temperature.

The treatment of the fibrous material may also be carried out in a large amount of liquid to product, typically from 1: 3 to 1: 100, preferably from 1: 4 to 1:25, and from 10 to 100 ° C, preferably from 60 to 98 ° C. In a liquid for about 1/4 to 3 hours, under conventional conditions, ie, under atmospheric pressure, in a conventional apparatus (eg, jigger, jet or winchbeck). If necessary, the heat treatment may also be carried out in an HT (high temperature) apparatus under pressure in a temperature range of 150 ° C. or lower, preferably 10 to 140 ° C.

In some cases, the fiber material is then sufficiently washed with hot water of 90 to 98 ° C., followed by washing with medium temperature water and finally cold water, and if necessary, after neutralizing and drying at elevated temperature.

In the following examples,% is always based on weight.

Preparation of individual components

Example 1 Preparation of Component (b)

In flasks equipped with a ground-glass stopper and heated jacket

360.0 g of deionized water,

76.0 g of 1 mol of C ₁₃ oxoalcohol and 9 mol of ethylene oxide

48 g of 1 mol of C ₁₃ oxoalcohol and 9 mol of ethylene oxide are charged at 20-30 ° C. and the contents of the flask are heated to 88-92 ° C. Milky turbid emulsion is obtained.

Subsequently, an initiator solution dissolved in 60.0 g of deionized water consisting of 124.0 g of acrylic acid and 0.75 g of potassium persulfate was simultaneously added at 90 ° C. Acrylic acid is added for 180 minutes and initiator solution is added for 195 minutes. The resulting polymer solution is then stirred for about 15-30 minutes and then cooled to 25 ° C. While maintaining in the cold phase, 9.7 g of sodium hydroxide 30% solution is added with stirring well below 70 ° C.

A clear colorless product is obtained.

Example 2: Preparation of Component (b)

In flasks with abrasive glass stoppers and heating jackets

346.0 g of deionized water and

The reaction product of 138.0 g of 1 mol C ₁₃ oxoalcohol and 9 mol of ethylene oxide is charged at 20-30 ° C. and the contents of the flask are heated to 88-92 ° C. Milky turbid emulsion is obtained.

Subsequently, an initiator solution dissolved in 60.0 g of deionized water consisting of 124.0 g of acrylic acid and 0.75 g of potassium persulfate was simultaneously added at 90 ° C. Acrylic acid is added for 180 minutes and initiator solution is added for 195 minutes. The resulting polymer solution is then stirred for about 15-30 minutes.

Subsequently, 13.9 g of magnesium hydroxide is stirred at 85 to 95 ° C and the resulting homogeneous solution is cooled to 25 ° C. While maintaining in the cold phase, 321.6 g of deionized water is added with stirring well below 70 ° C.

A clear colorless product is obtained.

Preparation of New Formulations

Example 3

Mix the following ingredients with stirring:

Reaction product of 24% of 1 mol C ₁₃ oxoalcohol with 6 mol of ethylene oxide,

22% of component (b) according to example 1,

2.4% disodium dicarboxyethyl cocopropylenediamine,

10% of 1 mol C ₁₂ fatty alcohol and 6 mol of ethylene oxide

Reaction product of propylene oxide of 4 mol,

7.2% of 1-hydroxy-1,1-ethanediphosphonic acid,

3% D-gluconic acid,

6% 2-methyl-2,4-pentanediol and

25.4% water.

Low viscosity transparent homogeneous product is obtained.

This formulation is used as a fabric auxiliary formulation in the alkaline pulping process, the alkaline washing process and the mercerising process.

Example 4

Mix the following ingredients with stirring:

Reaction product of 32% of 1 mol C ₁₃ oxoalcohol with 7 mol of ethylene oxide,

Reaction product of 8% of 1 mol C ₁₃ oxoalcohol with 6 mol of ethylene oxide,

28% of component (b) according to example 1,

2.4% disodium dicarboxyl ethyl cocopropylene diamine,

4.8% of 1-hydroxy-1,1-ethanediphosphonic acid,

3% D-gluconic acid,

6% 2-methyl-2,4-pentanediol and

14.6% water.

Low viscosity clear homogeneous product is obtained.

This formulation is used as a fabric auxiliary formulation in alkaline pulping processes, alkaline washing processes and mercer processing processes.

Example 5

Mix the following ingredients with stirring:

Reaction product of 32% of 1 mol C ₁₃ oxoalcohol with 6 mol of ethylene oxide,

40% of component (b) according to example 2,

1.8% disodium dicarboxyl ethyl cocopropylene diamine,

4.8% of 1-hydroxy-1,1-ethanediphosphonic acid,

3% D-gluconic acid,

8% 2-methyl-2,4-pentanediol and

10.4% water.

Low viscosity clear homogeneous product is obtained.

This formulation is used as a fabric auxiliary formulation in the alkaline pulping process, the alkyli washing process and the mercer processing process.

Example 6

Mix the following ingredients with stirring:

Reaction product of 15% of 1 mol C ₁₃ oxoalcohol with 3 mol of ethylene oxide,

Reaction product of 15% of 1 mol C ₁₃ oxoalcohol with 5 mol of ethylene oxide,

42% of component (b) according to example 1,

4% resin fat ampopolycarboxy glycinate,

Reaction product of 12% of 1 mol C ₁₀ fatty alcohol with 6 mol of ethylene oxide / 1 mol of methyl end capped butylene oxide,

6% 2-methyl-2,4-pentanediol and

6% water.

Low viscosity clear homogeneous product is obtained.

This formulation is used as a fabric auxiliary formulation in refining and bleaching processes.

Example 7

Mix the following ingredients with stirring:

Reaction product of 3.5% of 1 mol C ₁₃ oxoalcohol with 5 mol of ethylene oxide,

9.5% reaction product of 1 mol of C ₁₃ oxoalcohol with 6 mol of ethylene oxide,

Reaction product of 2% of 1 mol C ₁₃ oxoalcohol with 9 mol of ethylene oxide,

12.6% of component (b) according to example 1,

4% sodium salt of cumene-4-sulfonic acid,

2.5% magnesium digluconate and

65.9% water.

Low viscosity clear homogeneous product is obtained.

This formulation is used as a fabric auxiliary formulation in the pad steam peroxide bleaching process.

Example 8

Mix the following ingredients with stirring:

Reaction product of 15% of 1 mol C ₁₃ oxoalcohol with 6 mol of ethylene oxide,

20.7% of component (b) according to example 2,

4% sodium salt of cumene-4-sulfonic acid,

2.4% magnesium digluconate and

57.9% water.

Low viscosity clear homogeneous product is obtained.

This formulation is used as a fabric auxiliary formulation in the pad steam peroxide bleaching process.

Example 9

Mix the following ingredients with stirring:

Reaction product of 30% of 1 mol C ₁₁ oxoalcohol with 4 mol of ethylene oxide,

Instead of 42% of 1 mol of C ₁₃ oxoalcohol and 9 mol of ethylene oxide

To a reaction mixture of 1 mol C ₃ oxoalcohol and 6 mol ethylene oxide

Except for using, component (b) according to Example 1,

Reaction product of 48 g of 1 mol C ₁₃ oxoalcohol with 10 mol of ethylene oxide,

12% of 1 mol C ₁₀ fatty alcohol and 6 mol of ethylene oxide and 1 mol of methyl

Reaction product of end capped butylene oxide,

3% dodecyliminodipropionate disodium salt,

6% 2-methyl-2,4-pentanediol and

7% water.

Low viscosity clear formulations are obtained.

Example 10

Mix the following ingredients with stirring:

Reaction product of 30% of 1 mol C ₁₁ oxoalcohol with 4 mol of ethylene oxide,

Reaction of 42% 1 mol C ₁₃ oxoalcohol with 9 mol 10 mol ethylene oxide

Instead of product, 1 mol of C ₃ oxoalcohol and 8 mol of ethylene oxide

Except for using the reaction product according to Example 1

Component (b),

12% of 1 mol C ₁₀ fatty alcohol and 6 mol of ethylene oxide and 1 mol of methyl

Reaction product of end capped butylene oxide,

3% dodecyliminodipropionate disodium salt,

6% 2-methyl-2,4-pentanediol and

7% water.

Low viscosity clear formulations are obtained.

Example 11

Mix the following ingredients with stirring:

Reaction product of 30% of 1 mol C ₁₁ oxoalcohol with 4 mol of ethylene oxide,

Reaction of 42% 1 mol C ₁₃ oxoalcohol with 9 mol and 10 mol ethylene oxide

Instead of 1 mol of C ₃ oxoalcohol and 4 mol of ethylene oxide

Except for using the reaction product according to Example 1

Component (b),

12% of 1 mol ping C ₁₀ fatty alcohol and 6 mol of ethylene oxide and methyl terminal

Reaction product of capped butylene oxide,

3% dodecyliminodipropionate disodium salt,

6% 2-methyl-2,4-pentanediol and

7% water.

Low viscosity clear formulations are obtained.

Example 12

Mix the following ingredients with stirring:

Reaction product of 30% of 1 mol C ₁₁ oxoalcohol with 4 mol of ethylene oxide,

42% of component (b) according to example 2,

12% of 1 mol C ₁₀ fatty alcohol and 6 mol of ethylene oxide and 1 mol of methyl

Reaction product of end capped butylene oxide,

3% dodecyliminodipropionate disodium salt,

6% 2-methyl-2,4-pentanediol and

7% water.

Low viscosity opaque formulations are obtained.

Example 13

Mix the following ingredients with stirring:

Reaction product of 38% of 1 mol C ₁₃ oxoalcohol with 7 mol of ethylene oxide,

24% of component (b) according to example 1,

6 g citric acid monohydrate,

4.8% of 1-hydroxy-1,1-ethanediphosphonic acid

3% D-gluconic acid,

6% 2-methyl-2,4-pentanediol and

18.2% water.

Low viscosity clear formulations are obtained.

Application Example

Example 14 Alkaline Hydrolysis by Pad Steam Method

The raw cotton fabric is immersed on the pad at room temperature using a treatment solution of the following composition.

2 g / l of the fabric auxiliary formulation of Example 4 and

30 g / l NaOH (100%).

The liquid absorption rate is 100%. The product is treated with steam at 120 ° C. for 10 minutes in a steam system and then washed with hot water. A callout fabric excellent in water absorption is obtained.

Example 15 Low Temperature Pad Batch Peroxide Bleaching

The raw cotton fabric is immersed on the pad at room temperature using a treatment solution of the following composition.

2 g / l of the fabric auxiliary formulation of Example 5,

30 g / l NaOH (100%) and

50 mg / l hydrogen peroxide.

The liquid absorption rate is 100%. Products containing water are packaged in plastic sheets in batches and stored for 20 hours with slow rotation at room temperature. The product is then washed with hot water to obtain an absorbent fabric with high whiteness and low fiber damage.

Example 16: Pad Steam Peroxide Bleaching

The raw cotton fabric is sprayed at room temperature using a treatment solution of the following composition.

2 g / l of the fabric auxiliary formulation of Example 8,

40 g / l NaOH (100%) and

30 mg / l hydrogen peroxide (35%).

The fabric is sprayed, for example, in a Raco-Yet apparatus (manufactured by Rimisch-Kleinwefers). The liquid absorption rate is 140%. The product containing water is treated with saturated steam at 102 ° C. for 2 hours in a steam apparatus and then washed with hot water.

Absorbent fabrics with a high degree of whiteness and few fiber hands are obtained.

Claims (17)

10 to 60% by weight of the nonionic surfactant (a) of the general formula (1), 10 to 60% by weight of a reaction product (b) of at least one nonionic surfactant of formula (2) with an ethylenically unsaturated sulfonic acid, an ethylenically unsaturated carboxylic acid or anhydrides thereof, 4-20% by weight of hydrotropes (c), 0 to 20% by weight of the nonionic surfactant (d) of the general formula (3), 0-8% by weight of magnesium salt (e) of organic carboxylic acid, 0-30% by weight of a chelating agent or metal ion sequestrant (f), 0-10 wt% of a diol or polyol (g) and A multifunctional textile adjuvant formulation comprising 0 to 60% by weight of water (h), which must comprise at least one of components (e) to (g). In the above formula, R ₁ and R ₂ are each independently C ₈ -C ₂₂ alkyl or C ₈ -C ₂₂ alkenyl, R ₃ is hydrogen, C ₁ -C ₄ alkyl, a cycloaliphatic radical having 6 or more carbon atoms, or benzyl, R ₄ is C ₉ -C _l4 alkyl, R ₅ is C ₁ -C ₈ alkyl, alicyclic radical having 5 or more carbon atoms, lower alkylphenyl or styryl, Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently hydrogen, methyl or ethyl, provided that one of Y ₁ , Y ₂ , Y ₃ and Y ₄ must be hydrogen, "Alkylene" is an alkylene radical of 2 to 4 carbon atoms, m _l is an integer from 1 to 40, n ₁ is an integer from 1 to 60, p ₁ is an integer of 4 to 10, p ₂ is an integer of 0 to 8. The textile co-formulation according to claim 1, wherein component (a) is at least one nonionic surfactant of formula (4). In the above formula, R ₆ is C ₈ -C _l3 alkyl, Y ₅ is hydrogen or methyl, m ₂ is 3 to 15. The textile adjuvant formulation according to claim 1, wherein the ethylenically unsaturated carboxylic acid in component (b) is a monocarboxylic acid having 3 to 5 carbon atoms. 4. The textile adjuvant formulation of claim 3, wherein the monocarboxylic acid used in component (a) is acrylic acid. The fabric aid formulation of claim 1, wherein component (b) is a reaction product of 45 to 5 weight percent acrylic or methacrylic acid with 5 to 45 weight percent of at least one nonionic surfactant of formula (5). In the above formula, R ₇ is C ₈ -C ₁₈ alkyl, Y ₆ is hydrogen, methyl or ethyl, n ₂ is 1 to 40. The textile auxiliary formulation of claim 1 wherein component (c) is sodium cumene-4-sulfonate. The textile adjuvant formulation according to claim 1, wherein component (c) is disodium dicarboxyethyl cocopropylene diamine or resin fatty empopolycarboxyglycinate. The textile co-formulation according to claim 1, wherein component (d) is a nonionic surfactant of formula (8). In the above formula, R ₁₂ is C ₉ -C ₁₄ alkyl, R _l3 is C ₁ -C ₄ alkyl, Y ₇ , Y ₈ , Y ₉ and Y ₁₀ are each independently hydrogen, methyl or ethyl, provided that one of Y ₇ , Y ₈ , Y ₉ and Y ₁₀ is necessarily hydrogen, p ₃ and p ₄ are each independently an integer of 4 to 8. The textile aid formulation of claim 1 wherein component (e) is magnesium monogluconate or magnesium digluconate. A compound according to claim 1, wherein component (f) is prepared from a mixture of monomers and oligomers of formula (9) (f _l ), d-gluconic acid (f ₂ ), citric acid (f ₃ ) and aminophosphonic acid (f ₄ ) Textile auxiliary formulations consisting of the selected compound. In the above formula, Y ₇ is hydrogen or -COT ₁ , R _l4, X ₃ and T ₁ are each independently C ₁ -C ₄ alkyl, q _l is 1-16. The textile adjuvant formulation according to claim 10, wherein component (f) is D-gluconic acid. The textile adjuvant formulation according to claim 1, wherein component (g) is 2-methyl-2-pentanediol. The method of claim 1, 10 to 60% by weight of at least one nonionic surfactant (a) of the general formula (4), 10 to 60% by weight of the reaction product (b) of 5 to 45% by weight of at least one nonionic surfactant of formula (5) with 45 to 5% by weight of acrylic acid, 4-20% by weight of hydrotroping agent (c) selected from sodium cumene-4-sulfonate and dodecyliminodipropionate disodium salt, 0 to 20% by weight of nonionic surfactant (d) of the general formula (8), 0-8% by weight of magnesium monogluconate or magnesium digluconate (e), 0-30% by weight of D-gluconic acid (f) and A textile adjuvant formulation comprising 0 to 10% by weight of 2-methyl-2,4-pentanediol (g) and comprising at least one of components (e) to (g). In the above formula, R ₆ is C ₈ -C ₁₃ alkyl, R ₇ is C ₈ -C ₁₈ alkyl, R ₁₂ is C ₉ -C ₁₄ alkyl, R ₁₃ is C ₁ -C ₄ alkyl, Y ₅ is hydrogen or methyl, Y ₆ is hydrogen, methyl or ethyl, Y ₇ , Y ₈ , Y ₉ and Y ₁₀ are each independently hydrogen, methyl or ethyl, provided that one of Y ₇ , Y ₈ , Y ₉ and Y ₁₀ is necessarily hydrogen, m ₂ is 4 to 15, n ₂ is 1 to 40, p ₃ and p ₄ are each independently an integer of 4 to 8. The monomeric ethylenically unsaturated sulfonic acid, monomeric ethylenically unsaturated carboxylic acid or anhydrides thereof are reacted in the presence of a catalyst and at least one nonionic surfactant of the general formula (1) and / or general formula (2) and the pH is 4.5 14. A process for preparing the fabric auxiliary formulation as claimed in any one of claims 1 to 13, which comprises first preparing component (b) by adjusting the reaction temperature and then adding the remaining components until a homogeneous solution is obtained. . A method of wetting, washing and / or bleaching a fibrous material comprising treating the fibrous material in an aqueous medium in the presence of a fabric auxiliary formulation as defined in claim 1. The method of claim 15, wherein the fabric auxiliary formulation is used in an amount of 0.1 to 60 g / l per liter of liquid. A fiber material treated by the method according to claim 15.